DE1520084A1 - Process for the preparation of dispersions of synthetic polymers in organic liquids - Google Patents

Description

The priority of filing in the UK dated December 18, 1959 has been claimed.

The invention relates to a method for the production of modified.

Dispersions / synthetic polymers in organic liquids »

keiten .. ·

It was previously found that one could be in organic ! times can produce stable dispersions of synthetic polymers in which stabilizing solvatable Groups through primary chemical bonds to molecules that form an integral part of the dispersed particles, are bound. This is in contrast to using more common ones Stabilizing agents in which the stabilizing solvatable groups are indirectly attached to the dispersed particles are bound by groups which themselves are attached to the surface of the dispersed particles only by second order forces

are absorbed.

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BAD Of = MGlNAt

By solvable group is meant a group «the by the organic liquid in which the polymer is dispersed is being solvated.

A method for incorporating the solvatable groups in the dispersed particle consists in " precipitating the polymer in the organic liquid in the presence of a block or graft copolymer, one component of which is solvated by the organic liquid and another component is compatible with the polymer and is precipitated together with him. This co-precipitation leads to the fact that the compatible constituent inextricably tangled with the precipitated polymer chains and thus becomes an integral part of the particle. In this way, the solvatable constituent is irreversibly bound to the dispersed particle through the primary chemical bonds of the block or graft mixed polymer. This process can be carried out, for example, by precipitating a preformed polymer from a solution or by preparing the polymer in an organic liquid in which it is insoluble. The block or graft copolymer can be added as such or formed in place during the formation of the polymer to be dispersed.

Another method is to find the solvable Groups at irregular intervals on the chains of the to be dispersed To bind polymers directly. This direct bond to the polymer molecules leads through primary chemical bonds

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to a polymer that is stable by itself and iti Fo $ a stable. Dispersion precipitates. The precipitation can take place at the same time as the formation of the stable polymer with a nonsolvent, or the polymer can be prepared in a solution and precipitated in bulk. This process of incorporating the solvatable groups into the polymer through primary chemical bonds can be effected during the polymerization. By carrying out the polymerization in the presence of a compound comprising the solvatable group and an unsaturated group capable of polymerization, or knowing which solvatable groups are bound to active groups in the polymer after it has been formed in solution . _ ' ./'- ;.'

It is often erwünschti in -. 2UR dlspergierten synthetic ■ '"' polymers modification of an additive, HIe insert a Weiehmecher or a compatible polymeric material IMQ in especially the case when the dispersion Iti to use a tllJfcrzugEraischung and is desired aussar the Pigmentation of the dispersion Μέ to modify the properties of the coating film produced from the dispersion, e.g. with regard to hardness, flexibility, weather resistance, petrol

a homogeneous coating from the polymer layer is to be provided, the modifying substance should of course be compatible with the polymer. If its Affinity to the polymer is such that it is contractual,

BATH

he can also like that. Polymer in the organic liquid in the « be soluble; in fact it may be preferable »to de & Mechanism of film formation from the dispersed particles simplify * that in the dispersion the modifying substance in the dispersed particles and not in the organic Liquid is localized, i.e. insoluble in the latter is.

This requirement of insolubility in the organic Liquid creates difficulties in incorporating the modifier into the dispersion. Even if the Modifying substance can be brought into intimate contact with the dispersed polymer particles, is the diffusion * » speed into the polymer at temperatures below the Second-order transformation temperature is very low, and the Formation of a strongly modified layer on the outside of the polymer particles can mask the stabilizing groups and coagulate the dispersion.

It has now been found that when preparing a dispersion of a modified synthetic polymer in a organic liquid a modifying substance that is present in the continuous phase of the organic liquid insoluble is, are incorporated into the dispersed ^ oiymteileohen can by putting the polymer and modifying substance in the organic liquid precipitates together.

BATH 90S82271260

. When the dispersion .'stellt by simultaneous polymerization andi precipitation · in the continuous phase of the dispersion mfd © · * *** ■. is ", the abwandelnde material initially in de * mixture are dissolved the monomers and the continuous phase * and then in-where it is ground as the monomer content of this mixture to the polymer and accordingly decrease the solvent power of the mixture in the conversion, ι the abwandelnde substance absorbed into the polymer at daqeen formation and thus incorporated into the pearled particles. If a dropwise addition of the monomer is to be reversed, the modified substance can be dissolved in the monomer and the solution added to the reaction vessel.

Instead, the modifier can be used when the dispersion is made by precipitating a preformed polymer from a solution, be dissolved in the polymer solution which it then precipitated simultaneously with the polymer

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will,, . . .

In the case of a polar synthetic polymer such as polymethyl methacrylate which stabilizes with solvatable groups originating from degraded natural rubber and not in one polar solvent, like an aliphatic hydrocarbon « fabric, - dlspergle-rt, would become suitable plasticizers highly polar, low molecular weight materials, such as Dimethy! Phthalates and polymeric esters of high molecular weight / oils glycol sebacic acid esters with benzoic acid end groups and Olycol adipic acid esters with lauric acid end groups, count.

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Suitable compatible film-forming modifying substances sohliessen alkyd resins with a low oil content, for example lauric acid-modified glyceryl phthalate with 20 $ ulgeh & lt,

Epoxy resins and aminoplasts or nitrogen resins, for example urea formaldehyde »melamine formaldehyde and benzoguahidine formaldehyde, a.

In the case of a non-polar synthetic polymer such as polystyrene, that rod with groups derived from acrylic acid! " and dissolved in a polar solvent such as ethanol * is dispersed, a suitable plasticizer would be an alkyl » naphthalene »a halogen naphthalene a halogen diphenyl or a halogen paraffin wax »with a suitable halogen sub« · stituent is chlorine.

The dispersed polymer to be modified can be a homopolymer or interpolymer, but will be used in this specification consistently referred to as polymer,

typical polymers include those of styrene, vinyl * toluene, diviny! benzene / diisopropeny! benzene. Allyl acetate, Dlallyladipat, acrylonitrile, vinyl chloride, vinylidene chloride, Vinyl propionate, vinyl acetate, vinyl stearate and acrylates and methacrylates of aliphatic alcohols, such as ethyl, octyl, Lauryl and natural peet alcohols. Preferred Möhoraere for Use in the production of polymers are methyl methacrylate, ß »Kthoxyäthylmethacrylat, Kthylacrylat, Vinyl · = aoetat, acrylonitrile methacrylic acid and acrylic acid and amides

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of these acids. Combinations of the above monomers can be used used, and other typical materials * used for Use as mixed monomers are suitable «include Dlmethylltaconat, Dläthylmaleate, maleic anhydride and Allyl alcohol.

If the polymer dispersion is to be used as a coating mixture, it can be pigmented.

The invention is illustrated by the following examples. Parts are based on weight *

Example 1 ^f f / <■ - · _: '·

A polymer dispersion was prepared by adding a mixture of 1500 parts of methyl methacrylate, 3000 parts of mineral spirits, 40 parts of degraded rubber (reduced viscosity In'Benzol - 0.7) and 3 parts of benzoyl peroxide in a stirrer, cooling coil, thermometer, heating jacket and against the atmosphere entltlftetem cooler reaction vessel fitted was heated to 85 ⁰ C. After 5 hours the polymerization was complete and the moderate dispersion was cooled and allowed to react from the reaction.

in

the container removed,

An attempt was made / the dlsper-

Gated polymer a plasticizer up to a ratio of Incorporate polymer to plasticizer such as 100 s 33, with the. Plasticizers insoluble in white spirit. Dimethyl phthalate ver « was turned. When simply mixed, the latex thickened raseh and coagulated.

The experiment was repeated using an improver th process, whereby the plasticizer degrades very slowly Agitation was added to the dispersion. It was possible to incorporate all of the plasticizer without coagulation, however, after 48 hours of storage, the dispersion became thick and gradually gelled «

The preparation of the dispersion would be repeated with addition

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of 500 parts of dimethyl phthalate to the initial batch, In which it was soluble. The reaction was normal and it a satisfactory dispersion was formed which had a storage stability of over 3 months. .

Example 2

Example 1 was repeated using a polymeric ester waxing agent, polypropylene, which is insoluble in mineral spirits. glycoladipic acid ester with lauric acid end groups, instead of the Dlmethy! Phthalate. Similar results were obtained in all cases obtain.

Example 3 A non-aqueous dispersion with plasticizer content was used

manufactured as follows.

3000 parts of mineral spirits, 30 parts of dismantled rubber and 10 Parts of Benzoyjperoxyd were in the device of Example I. heated to 80 ° C. A solution of 330 parts of dimethylphthalet in 1000 parts of methyl methacrylate was. while! a time of Dropped into the reaction vessel for 4 hours, and the boil was stopped

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continued for another half hour. The product was from », cooled and filtered by a slight fibrous Freed coagulate and gave an excellent product with excellent Storability.

example k

Example 5 was repeated, but instead of dimethylphthalate a polyester plasticizer insoluble in white spirit was used. Similar results were obtained.

Example 5

The following batch was done in a heating mantle, stirrer and reflux condenser equipped 3 «liter glass reaction vessel given:

Parts by weight

Styrene 500

Ethyl alcohol 1000

Chlorinated paraffin wax

(with $ 42 combined chlorine content) 250

Benzoyl peroxide 7

Polyacrylic acid

(reduced viscosity in acetone 2.8) 25

It was heated to reflux for 4 hours, and after this time it had become a silvery, stable dispersion made of plasticized polystyrene.

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Example 6 & * '' -

The following substances were placed in an oil reaction vessel equipped with a stirrer, heating and cooling jackets, thermometer, monomer ventilation and inert gas line

Weight

Petroleum ether '

(Boiling range 100 ~ 120 ° C) 700

Beneoyl peroxide 67

Degraded natural rubber 10

Inert gas was introduced into the reaction vessel, and the The temperature of its contents was increased to 50 ° C.

In this hot mixture was a for 1 1/2 hours Mixture of the following substances dripped;

Parts by weight

* ■

Methyl methacrylate 100

Ethyl acrylate 80

Methacrylic acid 20

Pentaethyl ether de3 hexamethylol

melamins 50

Benzoyl peroxide '50

Half an hour after the addition had ended, the reaction was essentially complete, and a stable liquid dispersion with a fine particle size had formed. Films cast from this dispersion and ^{dried at 70 °} C. were

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soft, clear undlSsungsmittelempflndlieh, but were hard "tough by baking at 150 ⁰ C and solvent resistant.

Example 7 Xn a device similar to that used in Example 6

were given.

Bewlohtsteile Petroleum ether

(Boiling range 40-60 ° C) 1000

Laekbenzin 400 Benzoyl peroxide SO Degraded rubber 20

and heated to their reflux temperature of approximately 60 ° C. Through the reflux condenser, a mixture of.

Parts by weight Methyl methacrylate 200

ß ~ Ethoxyethyl methacrylate

Glycol monomethacrylate 40

"Epikote 828" epoxy resin 100

Benzoyl peroxide 80

given.

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A stable liquid dispersion formed which minutes after the addition was complete by vacuum distillation to a solids content of approximately 50%. The temperature never rose during the distillation. 60 ⁰ C.

1 $ of a high boiling amine was added as a catalyst to the dispersion, and at one-hour baking of a cast film at 150 ⁰ C a hard, tough lösungsmlttelbe "° continuous film was formed.

Patent claims s

BATHROOM OPIQINAt 909822/1260

Claims (1)

Pa ten t an s ρ r ü ehe * ', -; - 1.) Process for the preparation of synthetic dispersions Polymers,. "- in organic liquids, which by solvatable, to an integral part of the dispersed particle-forming molecules through primary chemical bonds bound groups are stabilized, characterized that a modifying agent disperses in the particles by co-precipitation in the organic liquid of the polymer and a modifying substance insoluble in the organic liquid is incorporated. 2.) The method according to claim 1, characterized in that the polymer in the presence of a block or graft copolymer » of soft one component compatible with the polymer / and is precipitated with Him and the other component riui * 3h the organic liquid is solvated and the Poljiserdisperßion stabilized * is precipitated. ... ; 5.) The method according to claim 2 _B, characterized in that the dispersion dureh Polymerlsiersn des ^ lonoiaärs in the organic ^:? LÜ3SigkeIfc in ö £,:, *; rn: arfc of the modifying substance and a «εolvatis 1 erable constituent and a group, which can enter into the polymerization with the monomer, containing compound is produced. . 909822 / 1Z60 152Qt84 * IA- ** ·) Process according to claim 3 * characterized in that the modifying substance is dissolved in a mixture of the organic liquid and the monomer to be polymerized. 5.) The method according to claim 3, characterized in that the modifier is dissolved in the monomer and gradually becomes an organic liquid during the course of the polymerization is admitted. 6.) The method according to any one of claims 1 to 5, characterized in that a plasticizer is used as a modifying substance the polymer is used .. 7.) The method according to any one of claims 1 to 5 "can thereby" = marks * that as a modifying substance with the polymer Compatible f transforming material is used. 8.) Method according to one of claims 1 to 5 *, characterized in that that a crosslinking agent is used as the modifying agent for the polymer. 9.) Method according to one of claims 1 to 8, characterized in that « draws. " that the polymer contains methyl methacrylate and the solvatable group is derived from degraded natural rubber - = - directs. 10.) The method according to claim 9, characterized in that the modifying substance is a plasticizer. ■. · / · ■■ "- BATH ORIGINAL 909822/1260 11 *) Method according to claim 9 » characterized in that d Vss "■ ■ ■ - Λ» · the modifying substance is an epoxy resin. . ~ 12.) The method according to claim 9 / characterized in that the modifying substance is an aminoplast or nitrogen resin. 13.) coating mixture, characterized by a content of one produced according to one of the preceding claims stable dispersion. . 9098 2 2/126